EP0133410B1 - Verfahren zur Herstellung von Tri(M-Sulfophenyl)Phosphin - Google Patents
Verfahren zur Herstellung von Tri(M-Sulfophenyl)Phosphin Download PDFInfo
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- EP0133410B1 EP0133410B1 EP84420110A EP84420110A EP0133410B1 EP 0133410 B1 EP0133410 B1 EP 0133410B1 EP 84420110 A EP84420110 A EP 84420110A EP 84420110 A EP84420110 A EP 84420110A EP 0133410 B1 EP0133410 B1 EP 0133410B1
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- Prior art keywords
- tpp
- tppts
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- mixture
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- ZBMZOFSLQIPSPW-UHFFFAOYSA-N 3-bis(3-sulfophenyl)phosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S(O)(=O)=O)C=2C=C(C=CC=2)S(O)(=O)=O)=C1 ZBMZOFSLQIPSPW-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000004519 manufacturing process Methods 0.000 title description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000011541 reaction mixture Substances 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- JPGXOMADPRULAC-UHFFFAOYSA-N 1-[butoxy(butyl)phosphoryl]oxybutane Chemical compound CCCCOP(=O)(CCCC)OCCCC JPGXOMADPRULAC-UHFFFAOYSA-N 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 239000000413 hydrolysate Substances 0.000 claims 4
- 238000006277 sulfonation reaction Methods 0.000 abstract description 23
- 239000003446 ligand Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000007037 hydroformylation reaction Methods 0.000 abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 abstract description 3
- 239000010948 rhodium Substances 0.000 abstract description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- 235000011149 sulphuric acid Nutrition 0.000 abstract 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 55
- MYAJTCUQMQREFZ-UHFFFAOYSA-K tppts Chemical compound [Na+].[Na+].[Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=C(C=CC=2)S([O-])(=O)=O)=C1 MYAJTCUQMQREFZ-UHFFFAOYSA-K 0.000 description 26
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- NTUROZDXWLPVHB-UHFFFAOYSA-M sodium;3-diphenylphosphanylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NTUROZDXWLPVHB-UHFFFAOYSA-M 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- -1 aldehyde compounds Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical class C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940093635 tributyl phosphate Drugs 0.000 description 2
- YQEPTNWSGJQCOK-UHFFFAOYSA-N 2-bis(2-sulfophenyl)phosphanylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1P(C=1C(=CC=CC=1)S(O)(=O)=O)C1=CC=CC=C1S(O)(=O)=O YQEPTNWSGJQCOK-UHFFFAOYSA-N 0.000 description 1
- BTVVFMGRXHONDV-UHFFFAOYSA-N 2-bis(2-sulfophenyl)phosphorylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1P(=O)(C=1C(=CC=CC=1)S(O)(=O)=O)C1=CC=CC=C1S(O)(=O)=O BTVVFMGRXHONDV-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- JROGBPMEKVAPEH-GXGBFOEMSA-N emetine dihydrochloride Chemical compound Cl.Cl.N1CCC2=CC(OC)=C(OC)C=C2[C@H]1C[C@H]1C[C@H]2C3=CC(OC)=C(OC)C=C3CCN2C[C@@H]1CC JROGBPMEKVAPEH-GXGBFOEMSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5054—Preparation; Separation; Purification; Stabilisation by a process in which the phosphorus atom is not involved
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/5095—Separation; Purification; Stabilisation
Definitions
- the present invention relates to a process for the preparation of tri (m-sulfophenyl) phosphine.
- Tri (m-sulfophenyl) phosphine (hereinafter referred to as TPPTS) is a known product, essentially used as a water-soluble ligand making it possible to form complexes with transition metals, for example rhodium, in water and these solutions can be used in particular as catalyst for the synthesis of aldehyde compounds by hydroformylation of olefins as it is written in the French patent 2 314 910. A synthesis is described in the French patent 2 314 910.
- Example 1 of this patent one prepares this product in the form of its sodium salt by sulfonation of triphenylphosphine (hereinafter referred to as TPP) with oleum at 20% by weight of sulfuric anhydride (SO 3 ).
- TPPMS triphenylphosphine
- TPPDS trisulfonated triphenylphosphine
- OTPPMS oxides of these three products
- the sulfonation reaction is then stopped by diluting the reaction medium with water. This gives a hydrolyzate rich in sulfuric acid and comprising the sulfonated triphenylphosphine in acid form.
- the hydrolyzate is neutralized, for example with sodium hydroxide, so as to decrease, by successive crystallizations, the sulphate anions in the form of sodium sulphate in an aqueous medium, then the sulphonated triphenylphosphine is crystallized under form of its sodium salt by addition of methanol and ethanol then evaporation of the solvent.
- triphenylphosphine If the sulfonation of triphenylphosphine is carried out at 30 ° C for about twenty hours, it is possible to isolate, after various successive crystallizations, a mixture containing 80% by weight of sodium salt of tri (sulfophenyl) phosphine and 20% in weight of sodium salt of tri (sulfophenyl) phosphine oxide.
- Example 2 of the certificate of addition 2,349,562 to the French patent 2,314,910 that for the TPPTS obtained in Example 2 of the main patent, the sulfonate substitution is located in the meta position.
- FR-A-2 532 318 a process for the manufacture of TPPTS similar to that described in French patent 2 314 910 is described except that the various sulfonated tri-phenylphosphines are extracted, before neutralization with sodium hydroxide.
- hydrolyzate obtained after stopping the sulfonation reaction by means of an extractant chosen in particular from phosphonic esters such as, for example, dibutyl butyl phosphonate or phosphoric esters such as, for example, tributyl phosphate.
- Example 4 of this patent application after having carried out the sulfonation of TPP with oleum at 20% S0 3 by weight in H 2 SO 4 , one obtains, after treatment with the extractant, mixture of 72.9% TPPTS, 17.1% TPPDS and 10% sulfonated triphenyl phosphine oxides. It is therefore seen that, during the sulfonation step, TPPDS is formed.
- TPPTS is the best of the ligands for forming a complex with rhodium and that TPPTS is then higher than TPPMS and TPPDS.
- TPPTS degree of oxidation of phosphorus P III
- the aim of the present invention is therefore to propose an industrial process for the preparation of TPPTS which no longer has the drawbacks of known processes and which makes it possible to obtain, during the first sulfonation step, a very high proportion of TPPTS with the least possible impurities.
- Another object of the present invention is to propose an industrial process for the preparation of TPPTS which makes it possible to have a trisulfonation rate (degree of oxidation of phosphorus P III ) as high as possible with an oxidation rate of the sulfonated products very low (degree of oxidation of phosphorus P v ).
- the TPPTS can be extracted from the hydrolyzate by any known method, for example by filtration and washing with methanol, as described in example 7 of French patent 2,314,910 or preferably by means of a liquid-liquid extraction such as described for example in application FR-A-2 532 318.
- the hydrolyzate and the extractant are brought into contact, an organic phase which contains TPPTS and a small amount of co-extracted sulfuric acid and an aqueous phase or raffinate is separated which contains sulfuric acid.
- alkylphosphates are used such as, for example, tributylphosphate or phosphonates such as dibutyl butylphosphonate.
- This purification method is particularly advantageous because the main impurity present when the sulfonation step implemented in accordance with the invention is stopped, is essentially OTPPTS.
- OTPPTS triphenylphosphine oxide
- This separation can be done by bringing the organic phase into contact with water if the TPPTS is to be obtained in the form of free acid, or with an aqueous solution containing an M + cation of mineral or organic origin if we want to obtain TPPTS in a salified form, for example by means of a sodium hydroxide solution.
- the temperature be between 15 and 25 ° C, preferably between 20 and 22 ° C. If the temperature is below 15 ° C the kinetics of the sulfonation reaction is too low .
- the molar ratio SO 3 / TPP is equal to at least 8 and preferably between 10 and 14, preferably between 10 and 12.
- a molar ratio of less than 8 does not cause the disappearance of TPPMS and TPPDS.
- the overall content by weight of SO 3 in the mixture (SO 3 + TPP + H 2 SO 4 ) hereinafter called ternary mixture, must be at least equal to 33% at the start of the reaction.
- the sulfonation reaction takes place in sulfuric acid as solvent and the weight content of H Z S0 4 in the ternary mixture is advantageously greater than or equal to 15% at the start of the reaction (i.e. a molar ratio H 2 S0 4 / TPP greater than or equal to 2.7) so that the viscosity of the medium is not too high for it to remain manipulated.
- the TPP is dissolved beforehand in sulfuric acid in an amount of at least 2.7 moles of H 2 SO 4 per mole of TPP, then the content is reached. by weight required in SO 3 relative to the ternary mixture by adding oleum having a high SO 3 content and / or freshly distilled liquid SO 3 .
- the addition of concentrated oleum and / or liquid SO 3 in the sulfuric solution is preferably carried out at a temperature in the region of 15 ° C, then the mixture is preferably brought to a temperature of 20-22 ° C.
- the duration of the sulfonation reaction must be sufficient for all of the starting TPP to be transformed into TPPTS.
- This duration essentially depends on the temperature of the reaction mixture, on the S0 3 content in the ternary mixture; this duration is all the longer as the temperature is lower and the S0 3 content lower. Those skilled in the art are able to choose this duration as a function of these parameters.
- a duration of approximately 46 hours is sufficient to obtain more than 99 mol% of P III of TPPTS.
- this duration must be of the order of 75 hours. Consequently, a content by weight of SO 3 in the ternary mixture greater than 40% is preferably used which requires only shorter reaction times, of the order of 45 hours and less.
- TPP 76.3 millimoles
- 2 g minimum 98% TPP FLUKA purum
- a homogeneous solution of TPP in sulfuric acid is then obtained.
- 112 g of 65% oleum are poured in 30 minutes with good stirring (SO 3 content: 0.91 mole).
- the bath temperature is then lowered to 10 ° C and poured slowly, while maintaining this temperature of 10 ° C, 16.4 g of distilled water (0.9 mole) in order to neutralize the excess SO 3 .
- the sulfonation reaction is carried out at 22 ° C for 52 hours.
- the temperature is then lowered to 10 ° C. and 7.1 g of distilled water (0.4300 mole) are poured in slowly while maintaining this temperature in order to neutralize the excess SO 3 .
- Curves (1) and (1) were obtained from the measurements carried out during the implementation of Example 1, curves (2) and (II) were obtained from the measurements carried out during the implementation of Example 2 and the curves (4) and (IV) were obtained from the measurements carried out during the implementation of Comparative Example 4.
- Example 2 The same apparatus is used as in Example 1, but the experimental conditions and the results obtained are collated in Table 2 below, in which X has the same meaning as in Table 1.
- Comparative examples 5 to 7 demonstrate that, if the content by weight of SO 3 in the ternary mixture is too low, it is not possible to achieve the aim of the invention (molar P III content of TPPTS relative to the sulfonated triphenylphosphines obtained greater than 99%).
- Comparative examples 8 and 9 show that it is necessary to have a molar ratio S0 3 / TPP at least equal to 8, preferably at least equal to 10, and comparative examples 10 and 11 show that a molar ratio S0 3 / TPP too low cannot be compensated by an increase in the sulfonation temperature.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Claims (11)
1. Verfahren zur Herstellung von Tri(m-sulfophenyl)phosphin (TPPTS) mittels Sulfonierung von Triphenylphosphin (TPP) mit einem H2S04-S03-Gemisch und anschließende Hydrolyse des Reaktionsgemisches, um die Sulfonierungsreaktion abzubrechen, dadurch gekennzeichnet, daß man, um ein an TPPTS sehr reiches Hydrolysat zu erhalten, die Sulfonierungsstufe unter folgenden Bedingungen durchführt:
- die Temperatur liegt zwischen 15 und 25°C,
- das Molverhältnis S03/TPP ist gleich oder größer als 8,
- der Anteil SO3 in dem Gemisch (SO3 + H2SO4 + TPP) zu Beginn der Reaktion beträgt 33 Gew.-% oder mehr.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Anteil an H2S04 in dem Gemisch (S03 + H2SO4 + TPP) zu Beginn der Reaktion 15 Gew.-% oder mehr ausmacht.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß die Temperatur 20 bis 22° C beträgt.
4. Verfahren nach Anspruch 1, 2 oder 3, dadurch gekennzeichnet, daß das Molverhältnis S03/TPP 10 bis 14 beträgt.
5. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß der Gesamtgehalt an S03 in dem Gemisch (S03 + H2S04 + TPP) zu Beginn der Reaktion mehr als 40 Gew.-o/o ausmacht.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß die Reaktionsdauer höchstens 45 Stunden beträgt.
7. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß das TPP, von dem ausgegangen wird, in praktisch reiner H2S04 gelöst und das S03 in Form von stark konzentriertem Oleum und/oder in Form von flüssigem S03 zugegeben wird.
8. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß der in Mol P des TPPTS angegebene prozentuale Anteil, bezogen auf die gesamten, im Hydrolysat enthaltenen, nicht-oxidierten sulfonierten Triphenylphosphine mindestens 99 % ausmacht.
9. Verfahren nach Anspruch 8, dadurch gekennzeichnet, daß der in Mol P des TPPTS angegebene prozentuale Anteil, bezogen auf die gesamten im Hydrolysat enthaltenen, oxidierten und nicht-oxidierten sulfonierten Triphenylphosphine, mindestens 85 % ausmacht.
10. Verfahren nach einem der vorangehenden Ansprüche, dadurch gekennzeichnet, daß das TPPTS von den im Hydrolysat enthaltenen Oxiden mittels flüssig-flüssig-Extraktion abgetrennt wird.
11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß man als Extraktionsmittel Tributylphosphat oder Dibutyl-butylphosphonat wählt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT84420110T ATE28877T1 (de) | 1983-08-03 | 1984-06-28 | Verfahren zur herstellung von tri(msulfophenyl)phosphin. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8312776 | 1983-08-03 | ||
| FR8312776A FR2550202B1 (fr) | 1983-08-03 | 1983-08-03 | Procede de preparation de tri(m-sulfophenyl) phosphine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0133410A1 EP0133410A1 (de) | 1985-02-20 |
| EP0133410B1 true EP0133410B1 (de) | 1987-08-12 |
Family
ID=9291357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84420110A Expired EP0133410B1 (de) | 1983-08-03 | 1984-06-28 | Verfahren zur Herstellung von Tri(M-Sulfophenyl)Phosphin |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4668824A (de) |
| EP (1) | EP0133410B1 (de) |
| JP (1) | JPS60100590A (de) |
| AT (1) | ATE28877T1 (de) |
| BR (1) | BR8403776A (de) |
| CA (1) | CA1219280A (de) |
| DE (1) | DE3465312D1 (de) |
| ES (1) | ES534819A0 (de) |
| FR (1) | FR2550202B1 (de) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4716250A (en) * | 1986-07-10 | 1987-12-29 | Union Carbide Corporation | Hydroformylation using low volatile/organic soluble phosphine ligands |
| US4731486A (en) * | 1986-11-18 | 1988-03-15 | Union Carbide Corporation | Hydroformylation using low volatile phosphine ligands |
| DE58909872D1 (de) * | 1988-12-02 | 2000-06-29 | Celanese Chem Europe Gmbh | Sulfonierte Phenylphosphane enthaltende Komplexverbindungen |
| IT1229512B (it) * | 1989-01-27 | 1991-09-03 | Eniricerche Spa | Procedimento per la idroformilazione catalitica di.olefine |
| DE4040314A1 (de) * | 1990-12-17 | 1992-06-25 | Hoechst Ag | Verfahren zur herstellung wasserloeslicher diphosphane |
| US5215667A (en) * | 1991-08-20 | 1993-06-01 | Exxon Chemical Patents Inc. | Method for separating water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction |
| US5288818A (en) * | 1991-08-20 | 1994-02-22 | Exxon Chemical Patents Inc. | Method for separating a water soluble noble metal catalyst from a noble metal catalyzed hydroformylation reaction |
| DE4328384A1 (de) * | 1993-08-24 | 1995-03-02 | Bayer Ag | Stabilisierte, flammwidrige Polycarbonatformmassen |
| DE4435190A1 (de) * | 1994-09-30 | 1996-04-04 | Hoechst Ag | Verfahren zur Herstellung von sulfonierten Arylphosphinen |
| DE4435171A1 (de) * | 1994-09-30 | 1996-04-04 | Hoechst Ag | 5-H-Phenyl(di-3,13-sulfonato)dibenzophosphol und ein Verfahren zu seiner Herstellung |
| US5817775A (en) * | 1996-10-10 | 1998-10-06 | Celanese International Corporation | Phosphines and catalysts containing the same |
| CN1046530C (zh) * | 1996-10-15 | 1999-11-17 | 中国石油化工总公司 | 三(间－磺酸盐苯基)膦的制备方法 |
| FR2787786B1 (fr) | 1998-12-23 | 2001-02-02 | Rhone Poulenc Fibres | Procede de preparation de composes organophosphores sulfones hydrosolubles et la realisation de reactions organiques avec catalyse biphasique |
| CN104045532B (zh) | 2013-03-15 | 2018-05-25 | 陶氏技术投资有限责任公司 | 加氢甲酰化方法 |
| CN103254232B (zh) * | 2013-05-27 | 2016-05-18 | 成都欣华源科技有限责任公司 | 水溶性三（间-磺酸盐苯基）膦的制备方法 |
| CN111808134B (zh) * | 2020-08-03 | 2022-08-12 | 山东京博石油化工有限公司 | 一种从磺化产物中提取三苯基膦磺酸盐的方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2314910A1 (fr) * | 1975-06-20 | 1977-01-14 | Rhone Poulenc Ind | Procede d'hydroformylation des olefines |
| FR2349562A2 (fr) * | 1976-04-29 | 1977-11-25 | Rhone Poulenc Ind | Procede d'hydroformylation des olefines |
| US4248802A (en) * | 1975-06-20 | 1981-02-03 | Rhone-Poulenc Industries | Catalytic hydroformylation of olefins |
| US4394322A (en) * | 1980-08-18 | 1983-07-19 | Gulf Research & Development Company | Group VA ylides and process for preparing same |
| US4507247A (en) * | 1980-11-24 | 1985-03-26 | Gulf Research & Development Company | Sulfonated Group Va ylides and process for preparing same |
| US4376870A (en) * | 1980-12-05 | 1983-03-15 | Monsanto Company | Optically active phosphine compounds |
| US4346236A (en) * | 1981-02-09 | 1982-08-24 | Fmc Corporation | Method of oxidizing tertiary-alkyl phosphines |
| DE3235030A1 (de) * | 1982-09-22 | 1984-03-22 | Ruhrchemie Ag, 4200 Oberhausen | Verfahren zur herstellung von sulfonierten arylphosphinen |
-
1983
- 1983-08-03 FR FR8312776A patent/FR2550202B1/fr not_active Expired
-
1984
- 1984-06-28 AT AT84420110T patent/ATE28877T1/de not_active IP Right Cessation
- 1984-06-28 DE DE8484420110T patent/DE3465312D1/de not_active Expired
- 1984-06-28 EP EP84420110A patent/EP0133410B1/de not_active Expired
- 1984-07-30 US US06/635,829 patent/US4668824A/en not_active Expired - Fee Related
- 1984-07-30 BR BR8403776A patent/BR8403776A/pt not_active IP Right Cessation
- 1984-08-02 ES ES534819A patent/ES534819A0/es active Granted
- 1984-08-02 CA CA000460274A patent/CA1219280A/fr not_active Expired
- 1984-08-02 JP JP59161650A patent/JPS60100590A/ja active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2550202A1 (fr) | 1985-02-08 |
| ES8504834A1 (es) | 1985-05-01 |
| BR8403776A (pt) | 1985-07-02 |
| ES534819A0 (es) | 1985-05-01 |
| JPH0421678B2 (de) | 1992-04-13 |
| US4668824A (en) | 1987-05-26 |
| JPS60100590A (ja) | 1985-06-04 |
| CA1219280A (fr) | 1987-03-17 |
| EP0133410A1 (de) | 1985-02-20 |
| FR2550202B1 (fr) | 1986-03-21 |
| DE3465312D1 (en) | 1987-09-17 |
| ATE28877T1 (de) | 1987-08-15 |
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